1,3,5-Triazinediones

ABSTRACT

1,3,5-Triazinediones of the formula ##SPC1## 
     Wherein X 1 , X 2 , R 1 , R 2  and R 3  are as hereinafter defined, are useful for the selective control of weeds in crops, e.g., corn. Many are also useful for altering plant flowering and plant sexual reproduction. 
     Exemplary of the class of compounds are 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione, 3-(p-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.

This application is a continuation of U.S. Pat. application Ser. No. 301,853, filed Oct. 30, 1972, now U.S. Pat. No. 3,855,219, granted Dec. 17, 1974, which is a continuation-in-part of application Ser. No. 268,767, filed July 3, 1972, which is in turn a continuation-in-part of application Ser. No. 181,202, filed Sept. 16, 1971, both now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to s-triazine herbicides.

Neumayer et al., "Pesticides", Chemical Week, Apr. 12 and 26, 1969, lists several commercial and experimental s-triazine herbicides. Among these are prometone and prometryne, which have the structural formulae: ##SPC2##

These and related compounds are disclosed in U.S. Pat. No. 2,909,420.

SUMMARY OF THE INVENTION

It has now been discovered that compounds of formula I are useful as selective herbicides for controlling broadleaf and grass weeds in such crops as rice, asparagus and corn. Many of the compounds are also useful, at lower rates of application, for altering plant flowering and plant sexual reproduction. ##SPC3##

Wherein

R₁ is alkyl of 1 through 8 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, cycloalkylalkyl of 4 through 7 carbon atoms, alkenyl of 3 through 4 carbon atoms, alkynyl of 3 through 4 carbon atoms, benzyl or ##SPC4##

Where

Y is hydrogen, halogen, alkyl of 1 through 4 carbon atoms, nitro, alkoxy of 1 through 4 carbon atoms, alkylthio of 1 through 4 carbon atoms, cyano or trifluoromethyl,

Z is hydrogen, halogen, methyl, ethyl, nitro, alkoxy of 1 through 4 carbon atoms, or alkylthio of 1 through 4 carbon atoms, and

Q is hydrogen, halogen, or methyl;

R₂ is hydrogen, a group ##EQU1## where A is alkyl of 1 through 3 carbon atoms or alkoxy or alkylthio of 1 through 4 carbon atoms, or a cation selected from lithium, sodium, potassium, calcium, magnesium, barium, or ##EQU2## where R₅, R₆ and R₇ can be the same or different and each can be hydrogen, alkyl of 1 through 4 carbon atoms, or hydroxy alkyl of 2 through 4 carbon atoms; and R₈ is hydrogen, alkyl of 1 through 12 carbon atoms, or benzyl; R₅ and R₆ can be taken together to form a ring that is --(CH₂)₂ --O--(CH₂)₂ - or -CH₂)_(n) -- where n is 4-6 and R₇ and R₈ are H;

R₃ is SR₄ or OR₄,

where

R₄ is alkyl of 1 through 6 carbon atoms,

cycloalkyl of 3 through 6 carbon atoms,

alkenyl of 3 through 4 carbon atoms,

alkynyl of 3 through 4 carbon atoms, or benzyl, and

X₁ and X₂ are oxygen or sulfur.

Preferred within the above formula because of ease of synthesis and higher herbicidal activity are the compounds where:

R₁ is alkyl of 3 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms;

R₂ is hydrogen;

R₃ is SR₄ or OR₄ ;

R₄ is alkyl of 1 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms; and

X₁ and X₂ are oxygen.

More preferred because of their highest herbicidal activity are those compounds of the formula where:

R₁ is alkyl of 3 through 4 carbon atoms;

R₂ is hydrogen;

R₃ is SCH₃, SC₂ H₅, OCH₃ or OC₂ H₅ ; and

X₁ and X₂ are oxygen.

Preferred herbicidal compounds within the above formula include:

3-tert-butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

3-sec-butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

3-isopropyl-6-methoxy-s-triazine-2,4(1H,3H)-dione

3-isopropyl-6-ethoxy-s-triazine-2,4(1H,3H)-dione

Preferred for altering plant flowering and/or plant sexual reproduction are those compounds of Formula I, R₄ is methyl or ethyl, Y is hydrogen, halogen or methyl, Z is halogen, and Q is hydrogen.

Most preferred for altering plant flowering and/or plant sexual reproduction are:

1. 3-(4-chlorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione

2. 3-(4-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

3. 3-(4-bromophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

4. 3-(3,4-difluorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

5. 3-(4-methylphenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

6. 3-(2-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

7. 3-(4-fluorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

8. 3-(2,4-dichlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

9. 3-(2-methylphenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione. ##EQU3## ##SPC5## wherein R₁, R₃, X₁ and X₂ are as previously defined.

The synthesis of allophanimidates and 3-thioallophanimidates from pseudourea and the synthesis of 1-thioallophanimidates and 1,3-dithioallophanimidates from thiopseudourea (Equation 1) can be performed analogous to a procedure given in Organic Synthesis 42, 87, which describes the preparation of methyl 4-phenyl-3-thioallophanimidate (1-phenyl-2-thio-4-methylisobiuret).

The reaction products of Equation (1) are reacted at about 0°-45°C in a solvent, e.g. methylene chloride, with one equivalent of a chloroformate or a chlorothiolformate in the presence of one equivalent of a base such as triethylamine (Equations 2a and 2b). After completion of the reaction, the methylene chloride solution is washed with water, dried, and the solvent evaporated to give alkoxycarbonylallophanimidates, alkylthiolcarbonylallophanimidates, alkoxycarbonylthioallophanimidates, alkylthiolcarbonylthioallophanimidates, alkoxycarbonyldithioallophanimidates and alkylthiolcarbonyldithioallophanimidates. Using a chlorodithioformate in the above reaction affords the corresponding alkylthiolthiocarbonylallophanimidates, alkylthiolthiocarbonylthioallophanimidates and alkylthiolthiocarbonyldithioallophanimidates.

The reaction products of Equation (2a) and Equation (2b ) are then refluxed for a sufficient time with a base such as sodium methoxide in methanol to effect cyclization (Equations 3a and 3b). The solvent is then evaporated under vacuum and the residue dissolved in water. Acidification of the aqueous solution usually precipitates the desired s-triazinediones, thio-s-triazinediones or s-triazinedithiones as an substantially pure solid.

The reaction products of Equations (2a) and (2b) are also obtained by reacting the pseudourea or thiopseudourea first with a chloroformate, a chlorothiolformate or a chlorodithioformate as in Equations (4a) and (4b), and then reacting the reaction products of Equations (4a) and (4b) with an isocyanate or isothiocyanate as in Equations (5a) and (5b). ##EQU4## wherein R₁, R₃, X₁ and X₂ are as previously defined.

Reacting the intermediate allophanimidates of equation (1) with phosgene or thiophosgene at temperatures of 0° to 100°C also gives the s-triazinediones of this invention: ##SPC6##

The s-triazinediones form salts which are useful alone or can be reacted with an acyl chloride, an alkyl chloroformate, or an alkyl chlorothiolformate to give 1-substituted analogs as illustrated by the following equations: ##SPC7## ##SPC8##

where A is an alkyl, alkylthio or alkoxy group.

The following examples are offered to illustrate the processes described above. All parts are parts by weight unless otherwise indicated.

EXAMPLE 1 3-tert-Butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

To a solution of 139 parts of 2-methyl-2-thiopseudourea sulfate in 1000 parts of 50% aqueous methanol at 0°C is added dropwise 88 parts of 50% sodium hydroxide, followed by 90 parts tert-butyl isocyanate in 200 parts tetrahydrofuran. The solution is concentrated at reduced pressure and filtered to yield, after drying, 90 parts of methyl 4-tert-butyl-1-thioallophanimidate melting at 102°-l04°C.

To a solution of 5.67 parts of the above compound and 4 parts of triethylamine in 50 parts methylene chloride at 0°C is added dropwise 3.3 parts methyl chlorothiolformate in 5 parts of methylene chloride. The solution is stirred overnight and washed once with water. After drying and evaporation of the solvent, there is obtained 3.8 parts methyl 4-tert-butyl-N-methylthiolcarbonyl-1-thioallophanimidate melting at 102°-105°C.

A solution of five parts of the above compound in 50 parts of methanol containing 3 parts of sodium methoxide is refluxed for one hour. The reaction mixture is then cooled and the methanol is evaporated at reduced pressure. One hundred parts of water are added and the solution twice extracted with 50 parts of ether. The aqueous layer is then neutralized at 0° to 5°C with hydrochloric acid and extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated to give 3 parts of 3-tert-butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione, melting at 112°-115°C.

EXAMPLE 2 3-Isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

To a solution of 69.5 parts of 2-methyl-2-thiopseudourea sulfate and 47 parts of methyl chloroformate in 1000 parts of water at 0°C is added dropwise 56.9 parts of potassium hydroxide in 200 parts of water. The reaction mixture is stirred at room temperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated at reduced pressure to give 45 g of methyl N-(1-amino-1-methylthiomethylene)carbamate melting at 72°-77°C.

A solution of seventy-four parts of the above compound and 47 parts of isopropyl isocyanate in 300 parts methylene chloride is stirred overnight. The solvent is evaporated to give 113.6 parts of methyl 4-isopropyl-N-methoxycarbonyl-1-thioallophanimidate melting at 129°-132°C.

A solution of one hundred parts of the above compound in 200 parts of methanol containing 27 parts of sodium methoxide is refluxed for one hour. The methanol is evaporated under vacuum and the residue dissolved in 200 parts of water. The aqueous solution is neutralized with hydrochloric acid to afford after filtration and drying 55 parts of 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione melting at 188°-90°C.

EXAMPLE 3 3-Methyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

To a solution of 69.5 parts of 2-methyl-2-thiopseudourea sulfate and 110 parts of methyl chloroethiolformate in 500 ml of water in added dropwise at 0°-5°C 120 parts of 50% sodium hydroxide. The reaction mixture is stirred at 0°-5°C for 1 hour and then at room temperature for 2 hours. The solution is then extracted with methylene chloride and the organic extract dried and evaporated under vacuum to give 47 parts of methyl N-(1-amino-1-methylthiomethylene)-thiolcarbamate melting at 75°-76°C.

To a solution of 8.2 parts of the above compound in 75 parts of methylene chloride is added 3.1 parts of methyl isocyanate. The reaction mixture is stirred at room temperature for 3 hours, and then the solvent evaporated under vacuum to give 10 parts of methyl 4methyl-N-methylthiolcarbonyl-1-thiolallophanimidate melting at 115°-117°C.

A solution of six parts of the above compound in 75 parts of methanol containing 4.5 parts sodium methoxide is refluxed for 1 hour. The methanol is evaporated and the residue dissolved in water. The aqueous solution is then neutralized with hydrochloric acid at 0°-5°C. The precipitate is collected by filtration and dried to give 2.3 parts of 3-methyl-6-methylthio-s-triazine-2,4(1H,3H)-dione melting at 243°-244°C.

EXAMPLE 4 3-(p-Chlorophenyl)-6-methylthio-s-triazine-2,4-(1H,3H)-dione

To a solution of 148 parts of methyl N-(1-amino-1-methylthiomethylene)-carbamate, prepared as in Example 2, in 2,000 parts methylene chloride is added 154 parts of p-chlorophenyl isocyanate. The reaction is stirred for 3 days. Then to it is added 54 parts of sodium methoxide in 540 parts of methanol. The reaction mixture is then refluxed for 1 hour. The reaction mass is cooled, and 2,000 parts of ether are added. The solid collected by filtration is dissolved in water and the solution neutralized with hydrochloric acid. The new solid thus formed is collected, dried, and recrystallized from ethanol/H₂ O to give 140 parts of 3-(p-chlorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione melting at 292°-295°C.

EXAMPLE 5 3-sec-Butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

To a solution of 7.2 parts of methyl N-(1-amino-1-methylthiomethylene)carbamate, prepared as in Example 2, in 50 parts of methylene chloride is added 5.5 parts of sec-butyl isocyanate. The reaction mixture is stirred overnight and the solvent evaporated to give 12 parts of crude methyl 4-sec-butyl-N-methoxycarbonyl-1-thioallophanimidate melting at 102°-104°C.

The above product is refluxed for 1 hour in 150 parts of methanol containing 6 parts of sodium methoxide. The solvent is evaporated under vacuum and the residue is dissolved in 100 parts of water. The aqueous solution is extracted with methylene chloride and the aqueous layer then neutralized at 0°-5°C with hydrochloric acid. The aqueous solution is extracted again with methylene chloride. The extract is dried and the methylene chloride evaporated to give 7 parts of a solid melting at 124°-132°C. Recrystallization from chlorobutane gives 4 parts of 3-sec-butyl-6-methylthio-s-triazine-2,4(1H,3H)-dione, melting at 133.5°-135.5°C.

EXAMPLE 6 3-(p-Chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

To 52 parts of 2-methylpseudourea hydrogen sulfate in 250 parts of water at 0°-5°C is added 31 parts of methyl chloroformate followed by dropwise addition of 74 parts of 50% sodium hydroxide. The reaction mass is stirred at room temperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated. The residue is triturated with hexane to give 23 parts of methyl N-(1-amino-1-methoxy-methylene)-carbamate melting at 36°-39.5°C.

To 13 parts of the compound prepared above in 200 ml of methylene chloride is added 15 parts of p-chlorophenyl isocyanate. The reaction mass is stirred overnight. The solvent is evaporated and the residue refluxed overnight in 100 parts of 10% sodium methoxide in methanol. Water is added and the solution neutralized with hydrochloric acid. The crude solid collected by filtration is recrystallized from acetonitrile to give 7 parts of 3-(p-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione melting at 238°-241°C.

EXAMPLE 7 3-(2-Methyl-4-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

To 20 parts of methyl N-(1-amino-1-methoxymethylene)-carbonate prepared as in Example 6 in 200 parts of methylene chloride is added 25 parts of 2-methyl-4-chlorophenyl isocyanate. It is stirred overnight and 8 parts sodium methoxide in 80 parts of methanol is added. It is refluxed for 1 hour and the solid is collected by filtration. It is dissolved in water and the solution neutralized at 0°-5°C. with concentrated hydrochloric acid. The precipitate is collected by filtration to give 25 parts of 3-(2-methyl-4-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione melting at 193°-195°C.

EXAMPLE 8 3-(o-Fluorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione

To a solution of 16 parts of methyl N-(1-amino-1-methylthiomethylene)carbamate, prepared as in Example 2, in 150 parts of methylene chloride is added 15 parts of o-fluorophenyl isocyanate. The reaction mixture is stirred overnight and the solvent evaporated to give after trituration with hexane 29 parts of methyl 4-(o-fluorophenyl)-N-methoxycarbonyl-1-thioallophanimidate melting at 123°-125°C.

Sixteen parts of the above product are refluxed for 1 hour in 150 parts of methanol containing 9 parts of sodium methoxide. The solvent is evaporated under vacuum and the residue is dissolved in 200 parts of water. The aqueous solution is extracted with methylene chloride and the aqueous layer then neutralized at 0°-5°C. with hydrochloric acid. The precipitate is collected and dried to give 11 parts of 3-(o-fluorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione melting at 196°-199°C.

EXAMPLE 9

The following s-triazinediones can be prepared by the procedure of Example 2 by substituting the listed 2-substituted thiopseudoureas and pseudoureas, for 2-methyl-2-thiopseudourea, by using various chloroformates and by replacing isopropyl isocyanate with various isocyanates or isothiocyanates.

    __________________________________________________________________________     Thiopseudourea Isocyanate or                                                   or Pseudourea  Isothiocyanate                                                                              Formates   s-Triazinediones                        __________________________________________________________________________     2-methyl-2-thiopseudourea                                                                     ethyl isocyanate                                                                            methyl chloroformate                                                                      3-ethyl-6-methylthio-s-triazine-2,4                                            -                                                                              (1H,3H)-dione, m.p.                                                            190-191°                         "              phenyl iso-  "          3-phenyl-6-methylthio-s-triazine-2,                                            4-                                                     cyanate                 (1H,3H)-dione, m.p.                                                            235-245°                         "              cyclohexyl iso-                                                                             "          3-cyclohexyl-6-methylthio-s-triazin                                            e-                                                     cyanate                 2,4(1H,3H)-dione, m.p.                                                         255-257°                         "              o-fluorophenyl                                                                              "          3-(o-fluorophenyl)-6-methylthio-s-t                                            ri-                                                    isocyanate              azine-2,4(1H,3H)-dione, m.p.                                                   196-199°                         "              o-nitrophenyl                                                                               "          3-(o-nitrophenyl)-6-methylthio-s-tr                                            i-                                                     isocyanate              azine-2,4(1H,3H)-dione, m.p.                                                   196-202°                         "              propyl iso-  "          3-propyl-6-methylthio-s-triazine-2,                                            4-                                                     cyanate                 (1H,3H)-dione, m.p.                                                            145-148°                         "              m-tolyl iso- "          3-(m-tolyl)-6-methylthio-s-triazine                                            -2,4-                                                  cyanate                 (1H,3H)-dione, m.p.                                                            176-180°                         "              allyl isocyanate                                                                            "          3-allyl-6-methylthio-s-triazine-2,4                                            (1H,3H)-                                                                       dione, m.p. 140-142°             "              3,4-dichlorophenyl                                                                          "          3-(3,4-dichlorophenyl)-6-methylthio                                            -s-tria-                                               isocyanate              zine-2,4(1H,3H)-dione, m.p.                                                    269-271°                         "              p-fluorophenyl iso-                                                                         "          3-(p-fluorophenyl)-6-methylthio-s-t                                            riazine-                                               cyanate                 2,4(1H,3H)-dione, m.p.                                                         239-243°                         "              p-nitrophenyl iso-                                                                          "          3-(p-nitrophenyl)-6-methylthio-s-tr                                            iazine-                                                cyanate                 2,4(1H,3H)-dione, m.p.                                                         279-280.5°                       2-methyl-2-thiopseudourea                                                                     p-bromophenyl                                                                               methyl chloroformate                                                                      3-(p-bromophenyl)-6-methylthio-s-tr                                            iazine-                                                isocyanate              2,4(1H,3H)-dione, m.p.                                                         272-273°                         "              o-chlorophenyl                                                                              "          3-(o-chlorophenyl)-6-methylthio-s-t                                            riazine-                                               isocyanate              2,4(1H,3H)-dione, m.p.                                                         212.5-214°                       "              m-chlorophenyl                                                                              "          3-(m-chlorophenyl)-6-methylthio-s-t                                            riazine-                                               isocyanate              2,4(1H,3H)-dione, m.p.                                                         192-195.5°                       "              cyclohexylmethyl                                                                            "          3-cyclohexylmethyl-6-methylthio-s-t                                            riazine-                                               isocyanate              2,4(1H,3H)-dione, m.p.                                                         177.5-178°                       2-allyl-2-thiopseudo-                                                                         isopropyl iso-                                                                              "          3-isopropyl-6-allylthio-s-triazine-                                            2,4-                                    urea           cyanate                 (1H,3H)-dione, m.p.                                                            140-142°                         2-methylpseudourea                                                                            phenyl isocyanate                                                                           "          3-phenyl-6-methoxy-s-triazine-2,4(1                                            H,3H)-                                                                         dione, m.p. 198-200°             "              cyclohexyl iso-                                                                             "          3-cyclohexyl-6-methoxy-s-triazine-2                                            ,4-                                                    cyanate                 (1H,3H)-dione, m.p.                                                            212-220°                         "              p-fluorophenyl                                                                              "          3-(p-fluorophenyl)-6-methoxy-s-tria                                            zine                                                   isocyanate              2,4(1H,3H)-dione, m.p.                                                         234-237°                         "              m-chlorophenyl                                                                              "          3-(m-chlorophenyl)-6-methoxy-s-tria                                            zine-                                                  isocyanate              2,4(1H,3H)-dione, m.p.                                                         183-185.5°                       "              m-fluorophenyl                                                                              "          3-(m-fluorophenyl)-6-methoxy-s-tria                                            zine-                                                  isocyanate              2,4(1H,3H)-dione, m.p.                                                         184-186°                         "              sec-butyl iso-                                                                              "          3-sec-butyl-6-methoxy-s-triazine-                      cyanate                 2,4(1H,3H)-dione, m.p.                                                         121-122.5°                       2-ethylpseudourea                                                                             p-chlorophenyl                                                                              methyl chloroformate                                                                      3-(p-chlorophenyl)-6-ethoxy-s-triaz                                            ine-2,4-                                               isocyanate              (1H,3H)-dione, m.p.                                                            241-242°                         2-methylpseudourea                                                                            p-nitrophenyl                                                                               "          3-(p-nitrophenyl)-6-methoxy-s-triaz                                            ine-2,4-                                               isocyanate              (1H,3H)-dione, m.p.                                                            290-292°                         "              p-bromophenyl                                                                               "          3-(p-bromophenyl)-6-methoxy-s-triaz                                            ine-2,4-                                               isocyanate              (1H,3H)-dione, m.p.                                                            208-210°                         "              3,4-dichloro-                                                                               "          3-(3,4-dichlorophenyl)-6-methoxy-s-                                            tria-                                                  phenyl iso-             zine-2,4(1H,3H)-dione, m.p.                                                    197-199°                                        cyanate                                                         2-methyl-2-thio-                                                                              phenyl isothio-                                                                             "          3-phenyl-6-methylthio-2-thio-s-tria                                            zine-                                   pseudourea     cyanate                 2,4(1H,3H)-dione, m.p.                                                         235-238°                         2-methylpsuedourea                                                                            p-methoxyphenyl                                                                             "          3-(p-methoxyphenyl)-6-methoxy-s-tri                                            azine-                                                 isocyanate              2,4(1H,3H)-dione, m.p.                                                         213-214°                         "              p-tolyl iso- "          3-(p-tolyl)-6-methoxy-s-triazine-2,                                            4-                                                     cyanate                 (1H,3H)-dione, m.p.                                                            225-226°                         "              benzyl iso-  "          3-benzyl-6-methoxy-s-triazine-2,4(1                                            H,3H)-                                                 cyanate                 dione, m.p. 169-170°             2-hexyl-2-thio-                                                                               propyl iso-  "          3-propyl-6-hexylthio-s-triazine-2,4                                            -                                       pseudourea     cyanate                 (1H,3H)-dione                           2-cyclopropyl-2-thio-                                                                         cyclopropyl iso-                                                                            "          3-cyclopropyl-6-cyclopropylthio-s-t                                            ri-                                     pseudourea     cyanate                 azine-2,4(1H,3H)-dione                  2-cyclohexyl-2-thio-                                                                          cyclooctyliso-                                                                              "          3-cyclooctyl-6-cyclohexylthio-s-tri                                            a-                                      pseudourea     cyanate                 zine-2,4(1H,3H)-dione                   2-allyl-2-thio-                                                                               cyclopropylmethyl                                                                           methyl chloroformate                                                                      3-cyclopropylmethyl-6-allylthio-s-      pseudourea     isocyanate              triazine-2,4(1H,3H)-dione               2-(3-methylallyl)-2-thio-                                                                     cyclohexylmethyl                                                                            methyl chlorothiol-                                                                       3-cyclohexylmethyl-6-(3-methylallyl                                            -                                       pseudourea     isocyanate   formate    thio)-s-triazine-2,4(1H,3H)-dione       2-propargyl-2-thio-                                                                           allyl isocyanate                                                                            methyl chloroformate                                                                      3-allyl-6-propargylthio-s-triazine-     pseudourea                             2,4(1H,3H)-dione                        2-(3-methylpropargyl)-                                                                        3-methylallyl                                                                               "          3-(3-methylallyl)-6-(3-methylpropar                                            gyl-                                    2-thiopseudourea                                                                              isocyanate              thio)-s-triazine-2,4(1H,3H)-dione       2-benzyl-2-thiopseudourea                                                                     propargyl iso-                                                                              "          3-propargyl-6-benzylthio-s-triazine                                            -                                                      cyanate                 2,4(1H,3H)-dione                        2-methylpseudourea                                                                            3-methlpropargyl                                                                            "          3-(3-methylpropargyl)-6-methoxy-s-                     isocyanate              triazine-2,4(1H,3H)-dione               2-hexylpseudourea                                                                             benzyl isocyanate                                                                           "          3-benzyl-6-hexyloxy-s-triazine-2,4-                                            (1H,3H)-dione                           2-methyl-2-thio-                                                                              p-iodophenyl iso-                                                                           methyl chlorodithio-                                                                      3-(p-iodophenyl)-6-methylthio-2-thi                                            o-                                      pseudourea     cyanate      formate    s-triazine-2,4(1H,3H)-dione             2-ethyl-2-thio-                                                                               m-tolyl isocyanate                                                                          "          3-(m-tolyl)-6-(ethylthio)-2-thio-s-     pseudourea                             triazine-2,4(1H,3H)-dione               -              p-butylphenyl                                                                               "          3-(p-butylphenyl)-6-ethylthio-2-thi                                            o-                                                     isocyanate              s-triazine-2,4(1H,3H)-dione             "              p-nitrophenyl                                                                               "          3-(p-nitrophenyl)-6-ethylthio-2-thi                                            o-                                                     isocyanate              s-triazine-2,4(1H,3H)-dione             "              o-methoxyphenyl                                                                             methyl chlorothiol-                                                                       3-(o-methoxyphenyl)-6-ethylthio-s-                     isocyanate   formate    triazine-2,4(1H,3H)-dione               2-ethyl-2-thio-                                                                               m-butoxyphenyl                                                                              methyl chlorothiol-                                                                       3-(m-butoxyphenyl)-6-ethylthio-s-       pseudourea     isocyanate   formate    triazine-2,4(1H,3H)-dione               2-methyl-2-thio-                                                                              p-methylthio-                                                                               "          3-(p-methylthiophenyl)-6-methylthio                                            -                                       pseudourea     phenyl iso-             s-triazine-2,4(1H,3H)-dione                            cyanate                                                         "              m-butylthiophenyl                                                                           "          3-(m-butylthiophenyl)-6-methylthio-                    isocyanate              s-triazine-2,4(1H,3H)-dione             "              p-cyanophenyl                                                                               "          3-(p-cyanophenyl)-6-methylthio-s-                      isocyanate              triazine-2,4(1H,3H)-dione               "              m-trifluoromethyl-                                                                          "          3-(m-trifluoromethylphenyl)-6-methy                                            l-                                                     phenyl iso-             thio-s-triazine-2,4(1H,3H)-dione                       cyanate                                                         "              3,5-dichlorophen-                                                                           methyl chloroformate                                                                      3-(3,5-dichlorophenyl)-6-methylthio                                            -s-                                                    yl isocyanate           triazine-2,4(1H,3H)-dione               "              p-bromo-m-chloro-                                                                           "          3-(p-bromo-m-chlorophenyl)-6-methyl                                            thio-                                                  phenyl iso-             s-triazine-2,4(1H,3H)-dione                            cyanate                                                         "              2-chloro-4-methyl-                                                                          "          3-(2-chloro-4-methylphenyl)-6-methy                                            lthio-                                                 phenyl iso-             s-triazine-2,4(1H,3H)-dione                            cyanate                                                         "              o-fluorphenyl                                                                               "          3-(o-fluorophenyl)-6-methylthio-s-t                                            ria-                                                   isocyanate              zine-2,4(1H,3H)-dione                   "              2-methyl-4-chloro-                                                                          "          3-(2-methyl-4-chlorophenyl)-6-methy                                            l-                                                     phenyl iso-             thio-s-triazine-2,4(1H,3H)-dione                       cyanate                                                         "              2-ethylhexyl "          3-(2-ethylhexyl)-6-methylthio-s-tri                                            a-                                                     isocyanate              zine-2,4(1H,3H)-dione                   2-ethylpseudourea                                                                             2-chloro-5-methoxy-                                                                         methyl chloroformate                                                                      3-(2-chloro-5-methoxyphenyl)-6-etho                                            xy-                                                    phenyl iso-             s-triazine-2,4(1H,3H)-dione                            cyanate                                                         "              3-methyl-4-bromo-                                                                           "          3-(3-methyl-4-bromophenyl)-6-ethoxy                                            -s-                                                    phenyl iso-             triazine-2,4(1H,3H)-dione                              cyanate                                                         "              2-bromo-4-nitro-                                                                            "          3-(2-bromo-4-nitrophenyl)-6-ethoxy-                                            s-                                                     phenyl iso-             triazine-2,4(1H,3H)-dione                              cyanate                                                         "              2-nitro-4-chloro-                                                                           "          3-(2-nitro-4-chlorophenyl)-6-ethoxy                                            -s-                                                    phenyl iso-             triazine-2,4(1H,3H)-dione                              cyanate                                                         "              2,4-dichlorophenyl                                                                          "          3-(2,4-dichloropehnyl)-6-ethoxy-s-                     isocyanate              triazine-2,4(1H,3H)-dione               2-methylpseudo-                                                                               2,4-dibromophenyl                                                                           "          3-(2,4-dibromophenyl)-6-methoxy-5-t                                            riazine-                                urea           isocyanate              2,4(1H,3H)-dione                        "              2,5-dichloro-4-                                                                             "          3-(2,5-dichloro-4-nitrophenyl)-6-me                                            thoxy-                                                 nitrophenyl iso-        s-triazine-2,4(1H,3H)-dione                            cyanate                                                         "              3,4-diethoxyphenyl                                                                          "          3-(3,4-diethoxyphenyl)-6-methoxy-s-                    isocyanate              triazine-2,4(1H,3H)-dione               "              2,4-difluorophenyl                                                                          "          3-(2,4-difluorophenyl)-6-methoxy-s-                    isocyanate              triazine-2,4(1H,3H)-dione               "              2,5-dimethoxyphenyl                                                                         "          3-(2,5-dimethoxyphenyl)-6-methoxy-s                                            -                                                      isocyanate              triazine-2,4(1H,3H)-dione               2-methylpseudo-                                                                               3,5-dinitrophenyl iso-                                                                      methyl chloroformate                                                                      3-(3,5-dinitrophenyl)-6-methoxy-s-t                                            ria-                                    urea           cyanate                 zine-2,4(1H,3H)-dione                   "              2-fluoro-4,6-dinitro-                                                                       "          3-(2-fluoro-4,6-dinitrophenyl)-6-me                                            thoxy-                                                 phenyl isocyanate       s-triazine-2,4(1H,3H)-dione             "              3-nitro-4-fluorophenyl                                                                      "          3-(3-nitro-4-fluorophenyl)-6-methox                                            y-s-                                                   isocyanate              triazine-2,4(1H,3H)-dione               "              2-methyl-4-methoxyphenyl                                                                    "          3-(2-methyl-4-methoxyphenyl)-6-meth                                            oxy-                                                   isocyanate              s-triazine-2,4(1H,3H)-dione             "              2-methoxy-4-nitrophenyl                                                                     "          3-(2-methoxy-4-nitrophenyl)-6-metho                                            xy-                                                    isocyanate              s-triazine-2,4(1H,3H)-dione             "              2,4,5-trichlorophenyl                                                                       "          3-(2,4,5-trichlorophenyl)-6-methoxy                                            -s-                                                    isocyanate              triazine-2,4(1H,3H)-dione               "              2,4,6-trimethylphenyl                                                                       "          3-(2,4,6-trimethylphenyl)-6-methoxy                                            -s-                                                    isocyanate              triazine-2,4(1H,3H)-dione               __________________________________________________________________________

EXAMPLE 10 3-Isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione.

To a solution of 138 parts of 2-methyl-2-thiopseudourea sulfate in 500 parts of water is added 80 parts 50% sodium hydroxide at 0°-10°C. One thousand parts of acetone are added, followed by a dropwise addition of 85 parts of isopropyl isocyanate at 0°C. The reaction mixture is allowed to warm to room temperature in 2 hours. The acetone is evaporated and the solid is filtered and dried to give 150 parts methyl 4-isopropyl-1-thioallophanimidate melting at 81°-85°C.

To a solution of 3.9 parts of phosgene in 100 parts of benzene is added dropwise 8.7 parts of the above compound in 50 parts of tetrahydrofuran. The reaction mixture is heated to reflux, cooled, and 16 parts of 50% sodium hydroxide in 100 parts of water added. After heating the solution to reflux, the benzene layer is discarded and the aqueous layer is neutralized with hydrochloric acid to give after filtration and drying 2 parts of 3-isopropyl-6-methylthio-s-triazine-2,4-(1H,3H)-dione melting at 188°-190°C.

EXAMPLE 11 Sodium 3-isopropyl-6-methylthio-s-triazine-2,4-(1H,3H)-dione

To a solution of 1.6 parts of sodium methoxide in 20 parts of methanol is added 6.6 parts of 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione. The solution is evaporated under vacuum and the white solid is triturated with methylene chloride and filtered to give 5.5 parts of sodium 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione melting above 300°C.

Similarly, the following s-triazinedione salts can be prepared by using the appropriate starting materials.

    Lithium  3-isopropyl-6-methylthio-s-triazine-2,4-                                       (1H,3H)-dione                                                         Potassium                                                                               3-isopropyl-6-methylthio-s-triazine-2,4-                                       (1H,3H)-dione                                                         Calcium  bis-3-(tert-butyl)-6-methylthio-s-triazine-                                    2,4(1H,3H)-dione                                                      Magnesium                                                                               bis-3-(tert-butyl)-6-methylthio-s-triazine-                                    2,4(1H,3H)-dione                                                      Barium   bis-3-(tert-butyl)-6-methylthio-s-triazine-                                    2,4(1H,3H)-dione                                                      Sodium   3-(m-trifluoromethylphenyl)-6-methylthio-s-                                    triazine-2,4(1H,3H)-dione                                             Sodium   3-cyclooctyl-6-methylthio-s-triazine-2,4-                                      (1H,3H)-dione, >300°C.                                         Sodium   3-(m-fluorophenyl)-6-methylthio-s-triazine-                                    2,4(1H,3H)-dione, >300°C. -Sodium 3-(2-methyl-5-chlorophen              yl)-6-methylthio-s-                                                            triazine-2,4(1H,3H)-dione, >300°C.                             Sodium   3-(3-chloro-4-methylphenyl)-6-methylthio-s-                                    triazine-2,4(1H,3H)-dione, >300°C.                             Sodium   3-(2,6-dichlorophenyl)-6-methylthio-s-tria-                                    zine-2,4(1H,3H)-dione, >300°C.                                 Sodium   3-(p-tolyl)-6-methylthio-s-triazine-2,4-                                       (1H,3H)-dione, >300°C.                                         Sodium   3-cycloheptyl-6-methylthio-s-triazine-2,4-                                     (1H,3H)-dione, >300°C.                                    

EXAMPLE 12 Ammonium 3-(p-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione

To a mixture of 10 parts of 3-(p-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione and 100 parts of methanol is added 1 part of ammonia gas at 20°C. The solution is stirred for 30 minutes and then evaporated under vacuum to give 10.6 parts of ammonium 3-(p-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione.

Similarly, the following s-triazinedione amine salts can be prepared by using the appropriate starting materials.

    __________________________________________________________________________     methylammonium                                                                              3-(p-chlorophenyl)-6-methoxy-s-triazine-                                       2,4(1H,3H)-dione                                                  tri-(2-hydroxy-                                                                             "                                                                 ethyl)ammonium                                                                 tri-(2-hydroxy-                                                                             3-isopropyl-6-ethoxy-s-triazine-2,4-                              ethyl)ammonium                                                                              (1H,3H)-dione                                                     dimethylammonium                                                                            "                                                                 ethylammonium                                                                               "                                                                 morpholinium "                                                                 piperidinium "                                                                 butylammonium                                                                               3-(p-chlorophenyl)-6-methylthio-s-triazine-                                    2,4(1H,3H)-dione                                                  di-sec-butyl-                                                                               "                                                                 ammonium                                                                       diethylammonium                                                                             "                                                                 propylammonium                                                                              "                                                                 hexahydro-   3-isopropyl-6-methoxy-s-triazine-2,4(1H,3H)-                      azepidinium  dione                                                             pyrrolidinium                                                                               "                                                                 tetraethylammonium                                                                          "                                                                 trimethylammonium                                                                           3-(2-methyl-4-chlorophenyl)-6-methoxy-s-                                       triazine-2,4(1H,3H)-dione                                         tetramethylammonium                                                                         "                                                                 dodecyltrimethyl-                                                                           "                                                                 ammonium                                                                       2-hydroxyethylammonium                                                                      "                                                                 benzylammonium                                                                              "                                                                 benzyltrimethyl-                                                                            "                                                                 ammonium                                                                       triethylammonium                                                                            "                                                                 __________________________________________________________________________

EXAMPLE 13 1-Acetyl-3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione

To 9.0 parts sodium 3-isopropyl-6-methylthio-s-triazine-2,4(1H,3H)-dione prepared as in Example 10 in 100 parts tetrahydrofuran can be added 3.1 parts acetyl chloride. The reaction can be refluxed for 5 hours and the solvent evaporated. Methylene chloride can be added to the residue and the solution can be washed with 1N sodium hydroxide and brine. After drying and evaporation of the solvent, the residue can be recrystallized from chlorobutane.

Similarly, the following s-triazinediones can be prepared by using appropriate starting materials.

    __________________________________________________________________________     Starting s-triazinedione                                                                      Halide  Product                                                 __________________________________________________________________________     3-isopropyl-6-methylthio-                                                                     butyryl 1-butyryl-3-isopropyl-                                  s-triazine-2,4(1H,3H)-                                                                        chloride                                                                               6-methylthio-s-tria-                                    dione                  zine-2,4(1H,3H)-dione                                   3-isopropyl-6-ethoxy-s-                                                                       methyl  1-methoxycarbonyl-3-                                    triazine-2,4(1H,3H)-                                                                          chloroformate                                                                          isopropyl-6-ethoxy-s-                                   dione                  triazine-2,4(1H,3H)-dione                               3-(p-chlorophenyl)-6-                                                                         methyl  1-methylthiolcarbonyl-3-                                methoxy-s-triazine-                                                                           chlorothiol-                                                                           (p-chlorophenyl)-6-methoxy-                             2,4(1H,3H)-dione                                                                              formate s-triazine-2,4(1H,3H)-                                                         dione                                                   "              n-butyl 1-butylcarbonyl-3-(p-                                                  chloroformate                                                                          chlorophenyl)-6-methoxy-                                                       s-triazin-2,4(1H,3H)-                                                          dione                                                   3-(2-methyl-4-chloro-                                                                         n-butyl 1-butylthiolcarbonyl-3-                                 phenyl)-6-methylthio-                                                                         chlorothiol-                                                                           (2-methyl-4-chlorophenyl)-                              s-triazin-2,4(1H,3H)-                                                                         formate 6-methylthio-s-triazine-                                dione                  2,4(1H,3H)-dione                                        __________________________________________________________________________

EXAMPLE 14 3-Isopropyl-6-methoxy-s-triazine-2,4(1H,3H)-dione

A solution of 23 parts of methyl N-(1-amino-1-methoxymethylene)-carbamate, 16 parts of isopropyl isocyanate 60 parts of methylene chloride, and a catalytic amount of dimethylformamide and triethylamine is allowed to stand at room temperature for 3 days. The solvent is evaporated to afford 33 parts of crude methyl 4-isopropyl-N-methoxycarbonyl-allophanimidate, an oil, N_(D) ²⁵ 1.4823.

A solution of 9 parts of the above compound, 10 parts of sodium methoxide, and 100 parts of methanol is refluxed for 1 hr. The solvent is removed under vacuum. Water is then added to the residue. After extraction with methylene chloride, the aqueous layer is neutralized at 5°-10°C. Filtration affords 3 parts of crude solid, which is recrystallized from acetonitrile to give 2 parts of 3-isopropyl-4-methoxy-s-triazine-2,4(1H,3H)-dione, m.p. 195°-200°C.

EXAMPLE 15 3-Isopropyl-6-ethoxy-s-triazine-2,4(1H,3H)-dione

To 114 parts of 2-methylpseudourea sulfate in 400 parts of water at 0°C is added 106 parts of 50% sodium hydroxide, followed by 400 parts of acetone, and 51 parts of isopropyl isocyanate. The reaction mixture is allowed to come to room temperature in 3 hrs. The organic solvent is then evaporated under vacuum, the aqueous residue saturated with sodium chloride, and the mixture extracted with methylene chloride. The organic extract is dried and the methylene chloride evaporated to yield 78 parts of methyl 4-isopropylallophanimidate, m.p. 64°-67°C.

To a solution of 32 parts of the above compound and 24 parts of triethylamine at 0°C is added 27 parts of ethyl chlorothiolformate. The reaction mixture is stirred at room temperature overnight. Water is added and the methylene chloride layer is separated and dried. The methylene chloride is then evaporated to yield 64 parts of crude methyl 4-isopropyl-N-ethylthiolcarbonylallophanimidate, an oil.

A solution of 64 parts of the above compound, 40 parts of sodium methoxide, and 500 parts of ethanol is refluxed for 1 hour. Ethanol is then removed under vacuum and water is added to the residue. After extraction with methylene chloride, the aqueous layer is neutralized at 5°-10°C. with concentrated hydrochloric acid to yield after filtration 8 parts of a solid, which is recrystallized from a mixture of carbontetrachloride/acetonitrile to give 2 parts of 3-isopropyl-6-ethoxy-s-triazine-2,4-(1H,3H)-dione, m.p. 170°-171°C. The methoxy group in the starting material is replaced by an ethoxy group during the reaction in the ethanol solvent.

Formulation and Use of the Compounds

The compounds of this invention are useful herbicides to selectively control weeds in crops such as field corn, sweet corn, rice, asparagus, established nursery stock and certain established fruit trees. The compounds can be applied preemergence, as a directed postemergence treatment or in certain specific cases as an overall postemergence treatment. Application rates range from 1/2 to 10 kilograms/hectare. Method and rate of application depend upon such factors, as crop, soil type, climatic condition and weed population. Uniform distribution of the compounds is important particularly in postemergence treatment.

These compounds may also be combined with other herbicides such as linuron, monuron, diuron, terbacil, and paraquat to control a broader spectrum of weeds.

The compounds of formula I can be formulated in the various ways which are conventional for herbicides of similar physical properties. Useful formulations include wettable and soluble powders, oil suspensions and solutions, aqueous dispersions, dusts, granules, pellets, and high strength compositions. Broadly speaking, these formulations consist essentially of about 1 to 99% by weight of herbicidally active material (including at least one compound of formula I in a herbicidally effective amount) and at least one of a) about 0.1 to 20% by weight of surface active agent and b) about 5 to 99% by weight of essentially biologically inert solid or liquid diluent. More specifically, the various types of formulations will generally contain these ingredients in the following approximate proportions.

    ______________________________________                                                      Percent By Weight                                                              Herbicide                                                                              Diluent   Surfactant                                      ______________________________________                                         Wettable Powders                                                                              25 - 90    0 - 74   1 - 10                                      Oil Suspensions or                                                             Solutions       5 - 35   55 - 94   1 - 10                                      Aqueous Dispersions                                                                           10 - 50   40 - 89   1 - 10                                      Dusts           1 - 25   70 - 99   0 - 5                                       Granules and Pellets                                                                           1 - 35   65 - 99   0 - 15                                      High Strength                                                                  Compositions   90 - 99    0 - 10   0 - 2                                       ______________________________________                                    

The actual percentages that can be realized with a particular compound of formula I will depend upon its physical properties.

The manner of making and using such herbicidal formulations is described in numerous patents. See, for example, Luckenbaugh U.S. Patent 3,309,192, Loux U.S. Pat. No. 3,235,357, Todd U.S. Patent 2,655,445, Hamm et al. U.S. Pat. No. 2,863,752, Scherer et al. U.S. Pat. No. 3,079,244, Gysin et al. U.S. Pat. No. 2,891,855, and Barrous U.S. Pat. No. 2,642,354.

The herbicidal activity of compounds of this invention was discovered in a greenhouse test. In this test, seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crus-galli), wild oats (Avene fatua), Cassia tora, morningglory (Ipomoea spp.), radish (Raphanus spp.), marigold (Tagetes spp.), dock (Rumex crispus), bean, corn, soybean, rice, wheat and nutsedge tubers were planted in a growth medium and treated preemergence with the chemical dissolved in a non-phytotoxic solvent. At the same time cotton having five leaves (including cotyledonary ones), johnsongrass (Sorghum halepense) having four leves, crabgrass and barnyardgrass with three leaves and nutsedge (Cyperus rotundus) from tubers with two leaves were treated postemergence. Bush beans with the third trifoliate leaf expanding and sorghum with four leaves were also treated postemergence. Treated plants and controls were maintained in a greenhouse for sixteen days, then all species were compared to controls and visually rated for responses to treatment. A qualitative (type of plant response) rating was made. The letter "C" indicates chlorosis; the letter "B" indicates burn; "G" indicates growth retardation; "D" indicates defoliation; "U" indicates unusual pigmentation; "S" indicates albinism; "I" indicates increased chlorophyll; "EF" indicates early flowering; "DF" indicates delayed flowering; "X" indicates axillary stimulation; "A" indicates growth acceleration; and "Y" indicates increased number of buds or flowers. A qualitative rating on a scale of 0 to 10 was also made; a rating of zero means no effect; a rating of 10 means maximum effect, e.g. complete kill in case of chlorosis. Results obtained in this test for some highly active compounds of this invention are given in the following table; in the table the ampersand symbol stands for the numeral 10.

                  POST EMERGENCE  PRE-EMERGENCE                                    Compound      1 2 3 4 5 6 7 8 5 6 8 9 2 10                                                                               11                                                                               12                                                                               13                                                                               14                                                                               15                                                                               7 16                                                                               17                                                                               18                                                                               19                 __________________________________________________________________________     3-(m-trifluoromethylphenyl-                                                                  11                                                                               3C                                                                               7B                                                                               5B                                                                               3B                                                                               7C                                                                               --                                                                               --                                                                               9C                                                                               9C                                                                               7C                                                                               &C                                                                               4C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               5C                                                                               4H                                                                               7C                                                                               6C 7G                6-methylthio-s-triazine-                                                       2,4(1H,3H)-dione, sodium                                                                     11  7D  5G                                8H                     salt          2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               &C                                                                               4C                                                                               7C                                                                               7C                                                                               6C                                                                               8C                                                                               1C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             9C                                                                             1C                                                                             1H                                                                               5C 4G                3-tert-butyl-6-methylthio-                                                                   11                                                                               3C                                                                               5C                                                                               6C                                                                               8C                                                                               9C                                                                               --                                                                               --                                                                               &E                                                                               8C                                                                               6G                                                                               &C                                                                               3G                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             9C                                                                             2G                                                                             9C                                                                               6C 7C                s-triazine-2,4(1H,3H)-                                                                       11                                                                               7G                                                             dione                                                                                        2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               &D                                                                               3B                                                                               9G                                                                               5G                                                                               3G                                                                               8C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             9C                                                                             0                                                                              5C                                                                               4C 5C                3-isopropyl-6-methylthio-                                                                    11                                                                               5C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               --                                                                               --                                                                               &C                                                                               &C                                                                               9C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      5C                                                                             8C                                                                             7C                                                                             8C                     s-triazine-2,4(1H,3H)-                                                                       2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               &C                                                                               2C                                                                               &C                                                                               &C                                                                               9C                                                                               &C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             &C                                                                             0                                                                              8C                                                                               7C &C                dione                                                                          3-ethyl-6-methylthio-s-                                                                      11                                                                               0 &C                                                                               7C                                                                               9C                                                                               9C                                                                               --                                                                               --                                                                               8C                                                                               9C                                                                               8C                                                                               &C                                                                               1C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               %C      &C                                                                             9C                                                                             2G                                                                             7C                                                                               6C 6C                triazine-2,4(1H,3H)-dione                                                                    2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               &C                                                                               1C                                                                               6G                                                                               0 3G                                                                               9C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             8C                                                                             0                                                                              6C                                                                               2C 7C                3-sec-butyl-6-methylthio-s-                                                                  11                                                                               3C                                                                               8C                                                                               7C                                                                               9C                                                                               &C                                                                               --                                                                               --                                                                               8C                                                                               &C                                                                               7C                                                                               &C                                                                               4C                                                                               &C                                                                               9C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             7C                                                                             0                                                                              7C                                                                               7C 5C                triazine-2,4(1H,3H)-dione                                                                    11  7D                                                                         2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               8C                                                                               3C                                                                               8C                                                                               5G                                                                               4C                                                                               &C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             8C                                                                             0                                                                              6C                                                                               4C 6C                3-cyclohexyl-6-methoxy-s-                                                                    11                                                                               6C                                                                               &C                                                                               2C                                                                               7C                                                                               &C                                                                               --                                                                               --                                                                               6G                                                                               &C                                                                               7G                                                                               9C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      9C                                                                             9C                                                                             3C                                                                             2S                                                                               4C 6C                triazine-2,4(1H,3H)-dione                                                                    11                                        6G                                   2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               9C                                                                               8C                                                                               5G                                                                               &C                                                                               6G                                                                               9C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      9C                                                                             7C                                                                             2C                                                                             1C                                                                               4C 7C                              2.2                                       5G                     3-(2-chlorophenyl)-6-                                                                        11                                                                               0 &C                                                                               2U                                                                               4C                                                                               6C                                                                               --                                                                               --                                                                               9C                                                                               &C                                                                               8C                                                                               &C                                                                               3C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             &C                                                                             4C                                                                             8C                                                                               5C 6C                methylthio-s-triazine-                                                                       2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               &C                                                                               2C                                                                               3C                                                                               9C                                                                               2C                                                                               9C                                                                               1C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             &C                                                                             0                                                                              4C                                                                               3C 4C                2,4(1H,3H)-dione                                                                             1.1                                                                              --                                                                               6C                                                                               --                                                                               --                                                                               --                                                                               9C                                                                               --                                                 3-isopropyl-6-methylthio-s-                                                                  11                                                                               8C                                                                               &C                                                                               9C                                                                               &C                                                                               &C                                                                               --                                                                               --                                                                               9C                                                                               &C                                                                               8C                                                                               9C                                                                               3C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             9C                                                                             5G                                                                             7C                                                                               6C                   triazine-2,4(1H,3H)-dione,                                                                   2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               &C                                                                               8C                                                                               9C                                                                               &C                                                                               7C                                                                               9C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             8C                                                                             0                                                                              7C                                                                               3C 6C                sodium salt                                                                    3-isopropyl-6-ethoxy-s-tria-                                                                 11                                                                               7C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               --                                                                               --                                                                               &C                                                                               &C                                                                               9C                                                                               &C                                                                               4C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             9C                                                                             7C                                                                             9C                                                                               8C 7C                zine-2,4(1H,3H)-dione                                                                        2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               9C                                                                               9C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             9C                                                                             1C                                                                             8C                                                                               5C 7C                              1.1                                                                              1C                                                                               8C                                                                               7C                                                                               5C                                                                               8C                                                                               --                                                                               --                                                               2.2                                                                              0 7C                                                                               5C                                                                               3C                                                                               6C                                                                               --                                                                               --                                                 3-isopropyl-6-methoxy-s-tria-                                                                11                                                                               8C                                                                               9C                                                                               9C                                                                               &C                                                                               &C                                                                               --                                                                               --                                                                               &C                                                                               &C                                                                               9C                                                                               &C                                                                               1C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      9C                                                                             9C                                                                             7C                                                                             8C                                                                               5C 8C                zine-2,4-1H,3H)-dione                                                                        2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               9C                                                                               7C                                                                               &C                                                                               9C                                                                               7C                                                                               &C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      9C                                                                             7C                                                                             2C                                                                             5C                                                                               4C 7C                3-isopropyl-6-allylthio-s-                                                                   11                                                                               2C                                                                               &C                                                                               8C                                                                               &C                                                                               &C                                                                               --                                                                               --                                                                               9C                                                                               &C                                                                               5C                                                                               &C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             7C                                                                             1C                                                                             5C                                                                               6C 7C                trizine-2,4(1H,3H)-dione                                                                     11                                                                               9G                                                                           2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               9C                                                                               7C                                                                               &C                                                                               &C                                                                               5C                                                                               9C                                                                               0 &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             8C                                                                             0                                                                              3C                                                                               2C 5C                              2.2                                                                              1C                                                                               9C                                                                               5C                                                                               5C                                                                               9C                                                                               --                                                                               --                                                               4.4                                                                              0 5C                                                                               2C                                                                               1C                                                                               4C                                                                               --                                                                               --                                                 3-(2-nitrophenyl)-6-methyl-                                                                  11                                                                               0 8C                                                                               2C                                                                               8C                                                                               5C                                                                               --                                                                               --                                                                               9C                                                                               &C                                                                               &C                                                                               &C                                                                               5C                                                                               &C                                                                               9C                                                                               &C                                                                               &C                                                                               &C      &C                                                                             8C                                                                             &C                                                                             5C                                                                               8C 6C                thio-s-triazine-2,4(1H,3H)-                                                                  2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               &C                                                                               6C                                                                               8C                                                                               5C                                                                               9C                                                                               9C                                                                               0 9C                                                                               &C                                                                               &C                                                                               7C                                                                               &C      8G                                                                             2C                                                                             9C                                                                             3C                                                                               6C 8C                              2.2                                       7G                                   2.2                                       7X                     3-(4-chlorophenyl)-6-                                                                        11                                                                               6C                                                                               7C                                                                               0 0 0 --                                                                               --                                                                               0 7C                                                                               4C                                                                               8C                                                                               7C                                                                               &C                                                                               &C                                                                               &C                                                                               &C                                                                               &C      9C                                                                             8C                                                                             5G                                                                             5C                                                                               2C 9C                methoxy-s-triazine-                                                                          11                                                                               EF                                                             2,4(1H,3H)-dione                                                                             2.2                                                                              --                                                                               --                                                                               --                                                                               --                                                                               --                                                                               5G                                                                               0 0 5C                                                                               0 7C                                                                               0 &C                                                                               &C                                                                               &C                                                                               7C                                                                               7C      6C                                                                             7C                                                                             0                                                                              1C                                                                               0  4C                              2.2         DF                                                                 2.2         Y                                                    __________________________________________________________________________      Footnotes                                                                       1 kg per hectare                                                               2 Nutsedge                                                                     3 Cotton                                                                       4 Johnson Grass                                                                5 Crabgrass                                                                    6 Barnyard Grass                                                               7 Bean                                                                         8 Sorghum                                                                      9 Wild Oats                                                                   10 Cassia                                                                      11 Morning Glory                                                               12 Mustard                                                                     13 Radish                                                                      14 Marigold                                                                    15 Dock                                                                        16 Corn                                                                        17 Soybean                                                                     18 Rice                                                                        19 Wheat                                                                 

The capability of preventing pollen formation (gametocidal activity) of 3-(p-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione is shown in the following tests:

A. Foliar sprays of 3-(p-chlorophenyl)-6-methoxy-s-triazine-2,4(1H,3H)-dione on Tenderette bush snap beans in the bud stage prevented fruit set 4 weeks with little effect on vegetative growth. Plants were about 23 days old and 25 to 30 cm tall when sprayed. Plants were passed under a fixed flat-spray nozzle calibrated to deliver 230 liters per hectare. Data from 3 greenhouse tests are summarized below:

                   Average Yield Per                                                              Plant at 4 wks                                                                                   Wt.                                           Rate   3 week        Number      of Fruit                                      kg/ha  Response Rating                                                                              of Fruit    (g.)                                          ______________________________________                                         1.1    2G, DF        O           O                                             .27    1X, 1I, DF    O           O                                             .07    O             2           1.8                                           0      O             16          45.9                                          ______________________________________                                    

B. Tiny Tim tomatoes with flower buds present were sprayed as above. One plant was treated at each rate and results are indicated below:

    Rate   Response Ratings                                                                             Number of Fruit Per Plant                                 kg/ha  19 Days  47 Days  19 Days                                                                               47 Days                                                                               73 Days                                 ______________________________________                                         1.1    3C, 2S   2C, 1A   O      O      O                                       .27    2C, IS   1C, 2A   O      O      1                                       .07    O        3A       O      O      12                                      0      O        O        5      21     20                                      ______________________________________                                    

C. Foliar sprays of corn prior to tasseling have shown control of pollen development and release. Anthers on plants treated at 4, 2 or 1 lb/A failed to open normally and pollen shed was delayed and reduced. 

We claim:
 1. A compound of the formula ##SPC9##wherein ##SPC10## where Y is halogen; R₂ is a cation selected from lithium, sodium, potassium, calcium, magnesium, barium, or ##EQU5## where R₅, R₆ and R₇ can be the same or different and each can be hydrogen, alkyl of 1 through 4 carbon atoms, or hydroxy alkyl of 2 through 4 carbon atoms; and R₈ is hydrogen, alkyl of 1 through 12 carbon atoms, or benzyl; R₅ and R₆ can be taken together to form a ring that is --(CH₂)₂ -O-(CH₂)₂ - or --(CH₂)_(n) - where n is 4-6 and R₇ and R₈ are H; R₃ is SR₄ or OR₄ where R₄ is methyl.
 2. A compound of claim 1 wherein:Y is chlorine, bromine or iodine; R₂ is sodium, ammonium, tri(2-hydroxyethyl) ammonium, trimethylammonium or benzylammonium; and R₃ is methoxy.
 3. The compound of claim 2 wherein:Y is chlorine and R₂ is tri-(2-hydroxyethyl) ammonium.
 4. The compound of claim 2 wherein:Y is chlorine and R₂ is sodium.
 5. The compound of claim 2 wherein:Y is chlorine and R₂ is ammonium.
 6. The compound of claim 2 wherein:Y is bromine and R₂ is tri-(2-hydroxyethyl) ammonium.
 7. The compound of claim 2 wherein:Y is bromine and R₂ is sodium.
 8. The compound of claim 2 wherein:Y is bromine and R₂ is ammonium.
 9. The compound of claim 2 wherein:Y is iodine and R₂ is tri-(2-hydroxyethyl) ammonium.
 10. The compound of claim 2 wherein:Y is iodine and R₂ is sodium.
 11. The compound of claim 2 wherein:Y is iodine and R₂ is ammonium. 